Manufacture of surface-active compounds



Patented Aug. 20, 1946 v 1 I 2,406,186 ,MANUFACTURE OF SURFACE-ACTIVE I 1 COMPOUNDS, q

' Alfred William Baldwin, Noel William-Cusaand Henry 'Worthington,

No Drawing. 'Applicationilanuaryiid,194Q8crial In Great BritainJanuarym30,

No. 472,388. 1942 Y 1 1 a .7 invention relates to the manufacture of new surface-active compounds. More particularly itlrelates to themanufacture of new ,sur-

Iace-active' condensation products of primary or secondary amines with particular,2,5-diketooxazolidines of the kindhereinafter specified,

We have now found that new surface-active compounds, useful as wetting agents, detergents, softeningx agents, emulsifying or dispersing agents are:obtained by causing; a primary or secondary amine to interact with oneot; more molecular proportions of a 2,5sdiketooxazolidine of. the for? mulay nN-oo-o herein R and B may each be a hydrogen atom or, onerof them; -but not both, maybe a methyl group, I r 1 V The 2,5 diketooxazolidines;which are used as startin ma erials may themselves be :made by I controllable rate. The optimum temperature (16- oausingan e-aminofoarboxylic acid-,ofi the ,for-; V

mula RNH-R'.C1I-ICOOH to react-with .a chloroformic ester CICOQX, whereby the compound XOCONRR'CHCOOI-I is formed, or by 65- terifyingth'ersaid acid andv then-treatin t Wi h carbon dioxide in; the cold -(in. the,,ma1nn,er de7 scribed in Nature,..l939, VQL AAJ D; 83-2) whereb the i-compound XOCO B'CHNB COOH is formed, the said compound xocoeuaeafou ooou" or XOCOR'CH'NR-'-C'OOH- being then treated with an agent adapted to convert acarboxylic acidinto the corresponding carboxylic halide, for example, a phosphorus halide or ox-yhalide, phosgene or thionyl chloride, followed by heating to effect ring closure and elimination of the halide X-Hal. In these formulae ;;stands for an alkyl, cycloalkyl or aralkylradical, n

' The u-amino acids from which may be derived the 2,5 diketooxazolidines which are to be used as starting materials for this invention are therefore glycine sarcosine and alanine. Oxazolidines l r ve m ra oi ?.1-

As suitable primary or secondary amines to iron; mixture of these a-amino acids be combinedwith the 2 ,'5 ;diketoo ;az olidines there may be mentioned, for examplqoctadecylamine,

a temperature that carbon d gide lis evolved at a Blackley, a, Manchester, I v England, assignors to Imperial Chemical Indusv tries-Limited, a corporationpf Greatpritain dioxidejhas slackened off,

oxazolidine is used pends .on the. particular oxazolidinefand amine used. "In practice it is convenient to heat the amine ,(to gether with the solvent, if one is used) and toadd the oxazolidine gradually making each subsequent addition when the evolution of carbon 1 it is belie'ved that the Jensen, 0: e u n ieeii-j lar proportions of amine and ,oxazolidine canjbe represented,'using a primary amine ANHz for? illustration, by'the equation A.NH: RN-C 0-0 A.NH.CO';CHR.NH.R e05 BL B- 500i When' 'inore than one 'rnolecularproportion oi the reactionis believed to jbe H; +nRi r-co-1o f= R':0HV('JO 7 A.Nn.ooonnwmo'oonngrrm,.-1.H +nool The following examples illustrate, but do not limi t, ,the invention. o The parts are by weight.

Example 1 26,9 partsof octadecylamine are dissolved at rid-{50C. in, 200 parts of dry benzene and. the solution isstirred and kept at that temperature while 11.5 parts of 3-methyl-2,5-diketooxazolidine are gradually added in portions, eachsuccessive evolution of carbon dioxide being allowedtocease beiqre the nextaddition is made The benzene is then removed by distillation, first at atmospheric pressure and finally under sub-atmospheric'pressure at C. There remains a paleyellow waxy solid which is only slightly soluble in hot water but completely soluble in dilute aqueous hydrochloric acid, forming a clear foaming olu ion. l l v Example 2 there remains a pale yellow, slightly hygroscopic;

:powder', which dissolves i hotlwater forming: a clear'foaming solut i i I H Example 3 34.5 seas of 3 -methyl-2 5,r-diketooxazolidine are-added to a solution oi5'.38 parts of octadecyla rline i n 400 parts, of dry benzene at l5--50f",Q.1in

V T a 1.1mm

clear solution. 7

r 3 r the way described in Example 1. The benzene is then distilled ofi, first at atmospheric pressure and then under sub-atmospheric pressure whereby thereisobtainedra'j'cream coloured powder;

which dissolves in" coldwateryfOrmirig a clear foaming solution. I

' Example 4 I 2,5-diketooxazolidine in the" mannerguescribeam 7' Example'l." The chloroformishistilledIoil', first-j; 7 7 I 5, parts of 4-methyl-2,5-diketooxazolidine are at atmospheric pressure and then under subatmospheric pressure whereby-. -there is obtained a light brown brittle powder wh'ich 'is easilysoluble in cold water forming a clear foaming solution.

. y Example 5 f" Te; fa solutidniof 7.3li ar o l y nfi 750, parts .of .dry chloroform at. 45550", f 0., 5.7.5

partslof- S-methyL-Zj diketooxaaolidine are ad ually added in themanner}. described inExample 1,, The chloroform iis then distilled; off, first at atmospheric pressure and then under sub-at mospheric pressure, whereby there is obtained a th i at on-i irr and keptv a that tem e easily dissolves in cold water, forming a clear solution. p

g I V Examplelll H r 7 wa i octadecylamine are dissolved in 25 parts of dry chloroform at 58-60 C. parts of 4-methyl-2,5-diketooxazolidine are added in portions, as described in Example 1.

The chlo- 'ro form is then' distilled 01f under sub-atmospheric pressure. There is thus obtained a cream coloured waxysolid. :which is soluble in hot waiter to givea clear-foaming solution.

ff'ff l ivample 11 7 added' in'portions in the manner described in -ligihtlbfown, hy ro'sopia-sticky gsolid which dis- 7 1 solves .easilyin' cold Water, ,ror' ingg 'clear lution which foams slightly on shaking:

of Nemethylcetylamineiare"dissolved at. 5: 9".iQqi fifiqarts oi;.;dry h rofprmzand ature while 23 partsof 3 methyl-2 5 diketooxa zolidine are gradually added in the way' described in Example 1. '4

ofl firstiat. .atmospheric pressure and then under sub-atmospheric. pressure. whereby there is btained an. orange. brittle powder. which dissolves in cold water, forming a clear foaming solution. E m l I "Toi ajsolution of 35 parts of 'cyclol'fxylamine in flfillparts of dry. chloroform at 45-50 C. there The chloroform is then distilled v ree'raauan added in me'w y described in Example11;.57.5 parts of. 3 methyl52,5 diketooxazolidiIlBJ QThe bhl'olofo rm is then. .distilledfofffirst at atmospheric pressure; and j-then" under sub-at mospheric pressure-a .There is thus obtained .a

pale brownish-yellow',"lhygroscopic powdenvvhich slightly foaming-solution. I I I t J "j :IExampZeB; V V V 57.5 parts" or 3-methyl 2,5-diktooxazolidine are added to a solution of 7.15 parts of p naphthylamine in 750 parts of dry chloroform at 45- 5Q C., the addition. being made graduallyflin the easilydissolves in cold-water forming a clear waydescribed in Example If. The chloroiorm is the r 'dis tilled'ofif, first at. atmospheric pressure and thniund er sub-atmospheric pressure where'- byflthere is obtained acream-coloured brittle powder which dissolves in hot water, forming. a

-"r i pms of piper'minedisoivea ii; 400 5mg of dry chloroform at 45-5 Q;Q.: there1 areadded" V 115 parts of 3-methyl-2,5-diketooxazolidine, the

addition being made Hithe -Way described in Example 1. The'chloroform is then, distilled .off

firstj at"atmosphericf pressure and then under.

u m e ic pressure; Therefiis; thuslobin parts of chloroform. When the evolution of carbon dioxide is complete, the chloroform is distilled ofi under sub-atmospheric.pressure. .1 .The

residue is then Washed with/ether;wherebyithereh is obtained, ajcream coloured waxy solidwhich 60 parts. of dry benzene, and 17.5 parts 'of 2,5411

k'etooxazolidine are added. The mixture 'is re: flux'ed-for 12'hour's. The benzene is. thenxdistilled off under sub atmospheric pressure; where-=- by-a cream coloured brittle" .solid is "obtained; 7 This is partiallyfsoluble in hot water to giveia hazy foaming solution...v l

i s mple-1s in S O parts fof' dry acetone at 45' 50 C;, 18.5 parts of 2.5-diketooxazolidinelare gradually added fin the manner described,in Example l." 'The acetone is'then distilled offunder sub-atmospheric pressure whereby there is obtained'a pale brown solidwhich dissolves in hot or cold waterfformthe above examples, and accordingly it is-to be drogen and methyl to a solution,,in aninert I organic solvent, of a monoamine having hydro{ gen on the amino nitrogen and having the remaining valencesof the nitrogen satisfied by by ,clrocarbon, -,the solution being heated to a temperaturesuflicientftoycauseievolution of carbon v dioxide on addition of the :diketooxa'zolidineand the -diketooXazolid iiie being I added as 1 evolution,

a n dio d s a k isiand 4 1 1 11 a -lea iene e 1 f mina ha bee a de s 1. e'-

movingthesolvent by distillation.

1 3 hev an tu jfs ifa active compounds which comprises gradually add:- ing '3-methyl-2.5-diketooxazolidine to a solution,

To 4.6 parts" orN-cetylmetliylamine dissolved in an inert organic solvent, of a primary alkylamine, the solution being heated to a temperature sufiicient to cause evolution of carbon dioxide on addition of the diketooxazolidineand the diketooxazolidine being added as evolution of carbon dioxide slackens and until at least one mol, per mol of amine, has been added, and removing the solvent by distillation. 3. The process for the manufacture of surface active compounds which comprises gradually adding a 2,5-diketooxazo1idine of the formula wherein one of R and R is hydrogen and the other is selected from the class consisting of hydrogen and methyl to a solution, in an inert organic solvent, of cetylamine, the solution being heated to a temperature sufiicient to cause evolution of carbon dioxide on addition of the diketooxazolidine and the diketooxazolidine being added as evolution of carbon dioxide slackens and until at least one mol, per mol of amine, has been added, and removing the solvent by distillation.

4. Process for the manufacture of surfaceactive compounds which comprises gradually adding a 2,5-diketooxazolidine of the formula and until at least one mol, per mol of amine, has been added, and removing the solvent by distillation.

5. Compounds of the formula wherein n is an integer from 1 to 30, R is hydrocarbon, A is selected from the class consisting of hydrogen and hydrocarbon, one of R and R is hydrogen and the other is selected from the class consisting of hydrogen and methyl.

6. Compounds of the formula wherein n is an integer from 1 to 30, R is hydrocarbon, A is selected from the'class consisting of hydrogen and hydrocarbon.

'7. Compounds of the formula R I-IN(-COCH2N CH3)-)1IH wherein n is an integer from 1 to 30 and R is alkyl.

8. Compounds of the formula C1sH3'1NH(-COCH2N(CH3) nH wherein n is an integer from 1 to 30. V

9. A compound having a chain containing from one to 30 units of the formula 

